日本长崎大学Keisuke Umakoshi团队揭示了铂络合物夹多核银团簇的流动行为和手性团簇光致发光特性。 相关研究成果发表在2021年2月22日出版的国际学术期刊《德国应用化学》。
研究人员合成了铂络合物夹多核银团簇，并通过单晶X射线衍射和核磁共振对其进行表征。三明治形多核银配合物在溶液中表现出两种不同类型的流动行为：铂配合物单元在Ag3核上的快速滑移和通过Cl阴离子和Ag离子处理的可逆脱金属-金属化反应。由Ag3络合物脱金属反应得到的Ag2络合物表现出从U到Z的异构化。这些多核银配合物表现出强烈的光致发光，其性质取决于Pt→Ag与格键的存在。被鉴定为“手性簇合物”的Ag3络合物通过与手性阴离子形成非对映异构盐进行光学拆分。
对映体表现出圆二色性（CD）和圆极化发光（CPL）特性，这对于手性三明治结构的化合物来说是前所未有的。通过理论计算可以了解它们的结构特征和光物理性质。
附：英文原文
Title: Multinuclear Ag Clusters Sandwiched by Pt Complex Units: Fluxional Behavior and Chiral‐at‐Cluster Photoluminescence
Author: Shinnosuke Horiuchi, Sangjoon Moon, Akitaka Ito, Jacopo Tessarolo, Eri Sakuda, Yasuhiro Arikawa, Guido H. Clever, Keisuke Umakoshi
Issue&Volume: 2021-02-22
Abstract: Multinuclear Ag clusters sandwiched by Pt complex units were synthesized and characterized by single crystal X‐ray diffraction and NMR studies. The sandwich‐shaped multinuclear Ag complexes showed two different types of fluxional behavior in solution: rapid slippage of Pt complex units on the Ag3 core and a reversible demetalation–metalation reaction by the treatment with Cl anion and Ag ion, respectively. The Ag2 complex obtained by demetalation reaction from the Ag3 complex displayed U to Z isomerization. These multinuclear Ag complexes showed strong photoluminescence whose properties depended on the existence of Pt→Ag dative bonds. The Ag3 complex, identified to be “chiral‐at‐cluster”, was optically resolved by the formation of a diastereomeric salt with a chiral anion. The enantiomers show circular dichroism (CD) and circularly polarized luminescence (CPL) properties which is unprecedented for compounds based on a chiral sandwich structure. Theoretical calculations allow to understand their structural features and photophysical properties.
DOI: 10.1002/anie.202101460
Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202101460
